Catalytic reactions using zeolites

ABSTRACT

A catalyst comprising a novel zeolite NU-87, is useful in a wide variety of hydrocarbon conversion reactions including isomerisation, transalkylation and alkylation.

The present invention relates to a novel zeolite hereinafter referred toas zeolite NU-87, to a method of making it, and to processes using it asa catalyst.

According to the present invention we provide a catalyst and processescatalysed thereby characterised by a zeolite, referred to hereinafter asNU-87, having a chemical composition expressed on an anhydrous basis, interms of the mole ratios of oxides, by the formula:

    100 XO.sub.2 : equal to or less than 10 Y.sub.2 O.sub.3 : equal to or less than 20 R.sub.2/n O

where

R is one or more cations of valency n,

X is silicon and/or germanium,

Y is one or more of aluminium, iron, gallium, boron, titanium, vanadium,zirconium, molybdenum, arsenic, antimony, chromium and manganese andhaving, in its as-prepared form, an X-ray diffraction pattern includingthe lines shown in Table 1.

The zeolite NU-87 may be present in the catalyst in its hydrogen form,designated H-NU-87, produced by calcination and/or ion exchange asdescribed herein. Zeolite H-NU-87 has an X-ray diffraction patternincluding the lines shown in Table 2.

                  TABLE 1                                                         ______________________________________                                        Zeolite NU-87 as-prepared                                                     d(Angstroms)    Relative Intensity.sup.(d)                                    ______________________________________                                        12.52       ± 0.15                                                                             w                                                         11.06       ± 0.15                                                                             s                                                         10.50       ± 0.15                                                                             m                                                         8.31        ± 0.15                                                                             w                                                         6.81        ± 0.12                                                                             w                                                         4.62        ± 0.10                                                                             m-s                                                       .sup.(a) 4.39 (Sh)                                                                        ± 0.10                                                                             m-s                                                       4.31        ± 0.10                                                                             vs                                                        4.16        ± 0.10                                                                             m                                                         3.98        ± 0.08                                                                             s-vs                                                      .sup.(b) 3.92 (Sh)                                                                        ± 0.08                                                                             s                                                         3.83        ± 0.08                                                                             w-m                                                       3.70        ± 0.07                                                                             m-s                                                       3.61        ± 0.07                                                                             w                                                         3.41        ± 0.07                                                                             m-s                                                       .sup.(c) 3.37 (Sh)                                                                        ± 0.07                                                                             m                                                         3.26        ± 0.06                                                                             s-vs                                                      3.15        ± 0.06                                                                             w                                                         3.08        ± 0.06                                                                             w                                                         2.89        ± 0.05                                                                             w-m                                                       2.52        ± 0.04                                                                             w-m                                                       ______________________________________                                         (Sh) denotes that the peak occurs as a shoulder on a more intense peak        .sup.(a) occurs on the low angle side of the peak at about 4.31A              .sup.(b) occurs on the high angle side of the peak at about 3.98A             .sup.(c) occurs on the high angle side of the peak at about 3.41A             .sup.(d) Based on a relative intensity scale in which the strongest line      in the Xray pattern is assigned a value of 100:                               weak (w) is less than 20                                                      medium (m) is between 20 and 40                                               strong (s) is greater than 40 but less than 60                                very strong (vs) is greater than 60.                                     

                  TABLE 2                                                         ______________________________________                                        ZEOLITE NU-87 IN ITS HYDROGEN FORM, H-NU-87                                   d(Angstroms)         Relative Intensity.sup.(d)                               ______________________________________                                        12.44                ± 0.15 w                                              11.12                ± 0.15 vs                                             10.52                ± 0.15 m-s                                            8.33                 ± 0.15 w                                              6.81                 ± 0.12 w-m                                            4.60                 ± 0.10 s-vs                                           .sup.(a) 4.39                                                                        (Sh)          ± 0.10 m-s                                            4.32                 ± 0.10 vs                                             4.17                 ± 0.10 m                                              3.98                 ± 0.08 vs                                             .sup.(b) 3.91                                                                        (Sh)          ± 0.08 s                                              3.84                 ± 0.08 w                                              3.73                 ± 0.07 m-s                                            3.60                 ± 0.07 w                                              3.41                 ± 0.07 s                                              .sup.(c) 3.37                                                                        (Sh)          doublet ±  0.07                                                                      m-s                                            3.34                                                                          3.26                 ± 0.06 vs                                             3.16                 ± 0.06 w-m                                            3.08                 ± 0.06 w-m                                            2.90                 ± 0.05 w-m                                            2.51                 ± 0.04 m                                              ______________________________________                                         (Sh) denotes that the peak occurs as a shoulder on a more intense peak        .sup.(a) occurs on the low angle side of the peak at about 4.32A              .sup.(b) occurs on the high angle side of the peak at about 3.98A             .sup.(c) occurs on the high angle side of the peak at about 3.41A             .sup.(d) Based on a relative intensity scale in which the strongest line      in the Xray pattern is assigned a value of 100:                               weak (w) is less than 20                                                      medium (m) is between 20 and 40                                               strong (s) is greater than 40 but less than 60                                very strong (vs) is greater than 60.                                     

In the diffractograms from which X-ray data are obtained some, or all,of the shoulders and doublets shown in Tables 1 and 2 may not beresolved from the stronger peaks with which they are associated. Thismay occur for poorly crystalline samples or in samples in which thecrystals are sufficiently small to result in significant X-raybroadening. It may also occur if the equipment, or conditions, used toobtain the pattern differ from those used herein.

The X-ray powder diffraction data provided herein were obtained with aPhilips APD 1700 automated X-ray diffraction system using Cu K-alpharadiation from a long fine focus X-ray tube operating at 40 KV and 50mA. The radiation was monochromatised by a curved graphite crystaladjacent to the detector. An automatic theta-compensating divergenceslit was used with a 0.1 mm receiving slit. Step scanned data werecollected between 1 and 60 degrees two-theta. The collected data wereanalysed in a DEC (Digital Equipment Corporation) Micro PDP -11/73computer with Philips PW 1867/87 version 3.0 software.

It is believed that NU-87 has a new framework structure or topologywhich is characterised by its X-ray diffraction pattern. NU-87 in itsas-prepared and hydrogen forms has substantially the X-ray data given inTables 1 and 2 respectively and is thereby distinguished from knownzeolites. In particular it is distinguished from zeolite EU-1, asdescribed in European Patent 42226, since the X-ray diffraction patternfor EU-1 does not contain an X-ray line at about 12.5 A. Furthermore theX-ray diffraction pattern for EU-1 contains an X-ray line at about 10.1A which line is absent from the X-ray diffraction patterns of NU-87.

Within the above definition of chemical composition the number of molesof Y₂ O₃ per 100 moles of XO₂ is typically in the range 0.1 to 10 forexample 0.2 to 7.5 and zeolite NU-87 appears to be most readily formedin a state of high purity when the number of moles of Y₂ O₃ per 100moles of XO₂ is in the range 0.4 to 5.

This definition includes as-prepared NU-87 and also forms of itresulting from dehydration and/or calcination and/or ion exchange. Theexpression "as-prepared" means the product of synthesis and washing withor without drying or dehydration. In its as-prepared form NU-87 mayinclude M, an alkali-metal cation, especially sodium and/or ammoniumand, when prepared for example from alkylated nitrogen compounds, mayinclude nitrogen-containing organic cations as described below ordegradation products thereof or precursors thereof. Suchnitrogen-containing organic cations are hereinafter referred to as Q.

Thus zeolite NU-87, as-prepared, has the following molar composition,expressed on an anhydrous basis:

    100 XO.sub.2 : less than or equal to 10 Y.sub.2 O.sub.3 : less than or equal to 10 Q: less than or equal to 10 M.sub.2 O

where Q is the nitrogen-containing organic cation referred to above andM is the alkali metal and/or ammonium cation.

The compositions for NU-87 above are given on an anhydrous basis,although as-prepared NU-87 and activated forms of NU-87 resulting fromcalcination and/or ion exchange may contain water. The molar H₂ Ocontent of such forms, including as-prepared NU-87, depends on theconditions under which it has been dried and stored after synthesis oractivation. The range of molar quantities of contained water istypically between 0 and 100 per 100 XO₂.

Calcined forms of zeolite NU-87, include no nitrogen-containing organiccompound or less than the as-prepared form, since the organic materialis burned out in the presence of air, leaving hydrogen ion as the othercation.

Among the ion-exchanged forms of zeolite NU-87 the ammonium (NH₄ ⁺) formis of importance since it can be readily converted to the hydrogen formby calcination. The hydrogen form and forms containing metals introducedby ion exchange are described below. Under some circumstances exposureof the zeolite of the invention to acid can result in partial orcomplete removal of a framework element such as aluminium as well as thegeneration of the hydrogen form. This can provide a means of alteringthe composition of the zeolite material after it has been synthesised.

Zeolite NU-87 may also be characterised by its sorptive capacity formolecules of various sizes. Table 3 contains sorption results which wereobtained on the hydrogen form of zeolite NU-87, the product from example6.

The data were obtained using a McBain-Bakr spring balance for water andmethanol and a CI Robal Microbalance for all other sorbates. Sampleswere outgassed at 300° C., overnight, before measurements were made.Results are presented as % (w/w) uptake at relative pressures (P/Po)where Po is the saturated vapour pressure. The figures for apparentvoidage filled were calculated assuming that the liquids maintain theirnormal densities at the sorption temperature.

                                      TABLE 3                                     __________________________________________________________________________    Sorption data for H-NU-87                                                            Adsorption                                                                    Temperature                                                                          Relative       Apparent Voidage.sup.1                                                                  Kinetic Diameter.sup.2                 Sorbate                                                                              [°C.]                                                                         Pressure                                                                           Uptake [% (w/w)]                                                                        filled [cm.sup.3 g.sup.-1 ]                                                             nm                                     __________________________________________________________________________    Water  25.4   0.07 5.4       0.054     0.265                                                0.28 8.3       0.083                                                          0.46 10.0      0.100                                            Methanol                                                                             25.2   0.10 10.3      0.130     0.380                                                0.29 11.6      0.147                                                          0.50 12.3      0.156                                            n-Hexane                                                                             26.7   0.13 11.0      0.167     0.430                                                0.31 11.5      0.175                                                          0.52 12.0      0.182                                            Toluene                                                                              26.7   0.11 12.3      0.142     0.585                                                0.32 13.2      0.152                                                          0.48 13.6      0.157                                            Cyclohexane                                                                          26.7   0.12 11.6      0.149     0.600                                                0.37 12.2      0.157                                                          0.49 12.5      0.160                                            Neopentane                                                                           0.0    0.11 3.29      0.05      0.620                                  (2,2-dimethyl 0.32 5.55      0.09                                             propane)      0.54 8.54      0.14                                             __________________________________________________________________________     .sup.1 The apparent voidage filled was calculated assuming the liquids        maintain their normal densities at the adsorption temperature                 .sup.2 Kinetic diameters are taken from "Zeolite Molecular Sieves", D W       Breck, J Wiley and Sons, 1976 p636. The value for methanol was assumed to     be the same as for methane, nhexane the same as nbutane and toluene the       same as benzene.                                                              .sup.3 The uptake is grams of sorbate per 100 grams of anhydrous zeolite.

The kinetic diameters given in the extreme right hand column of Table 3were taken from "Zeolite Molecular Sieves" D W Breck, J Wiley and Sons,1976 (p636), with the value for methanol assumed to be the same as formethane, the value for n-hexane to be the same as for n-butane and forvalue for toluene to be the same as for benzene.

The results show that NU-87 has significant capacity for varioussorbates at low partial pressures. The low uptake for water, comparedwith methanol, n-hexane, toluene and cyclohexane, indicates that NU-87has significant hydrophobic character. The results in Table 3 indicatethat zeolite NU-87 shows a molecular sieving effect with respect toneopentane since much lower uptakes were observed compared with theother hydrocarbon sorbates at similar relative pressures. In additionthe time required to reach equilibrium was much longer than for theother hydrocarbon sorbates. These results indicate that NU-87 has awindow size close to 0.62 nanometers.

The invention also provides a method for the preparation of zeoliteNU-87 which comprises reacting an aqueous mixture comprising a source ofat least one oxide XO₂, optionally a source of at least one oxide Y₂ O₃,optionally a source of at least one oxide M₂ O and at least onenitrogen-containing organic cation Q, or precursors thereof, the mixturepreferably having the molar composition:

XO₂ /Y₂ O₃ at least 10, more preferably 10 to 500, most preferably 20 to200

(R_(1/n))OH/XO₂ is 0.01 to 2, more preferably 0.05 to 1, most preferably0.10 to 0.50

H₂ O/XO₂ is 1 to 500, more preferably 5 to 250, most preferably 25 to 75

Q/XO₂ is 0.005 to 1, more preferably 0.02 to 1, most preferably 0.05 to0.5

L_(p) Z/XO₂ is 0 to 5, more preferably 0 to 1, most preferably 0 to 0.25

where X is silicon and/or germanium, Y is one or more of aluminium,iron, boron, titanium, vanadium, zirconium, molybdenum, arsenic,antimony, gallium, chromium, manganese, R is a cation of valency n whichcan include M, (an alkali metal cation and/or ammonium), and/or Q, (anitrogen-containing organic cation, or a precursor thereof). In somecircumstances it may be an advantage to add a salt L_(p) Z where Z is ananion of valency p and L is an alkali metal or ammonium ion which may bethe same as M or a mixture of M and another alkali metal or an ammoniumion necessary to balance the anion Z. Z may comprise an acid radicaladded for example as a salt of L or as a salt of aluminium. Examples ofZ may include strong acid radicals such as bromide, chloride, iodide,sulphate, phosphate or nitrate or weak acid radicals such as organicacid radicals, for example citrate or acetate. While L_(p) Z is notessential, it may accelerate the crystallisation of zeolite NU-87 fromthe reaction mixture and may also affect the crystal size and shape ofNU-87. The reaction is continued until it contains a major proportioni.e. at least 50.5% of zeolite NU-87.

Many zeolites have been prepared using nitrogen-containing organiccations or degradation products thereof or precursors thereof and inparticular, polymethylene alpha omega-diammonium cations having theformula:

    [(R.sub.1 R.sub.2 R.sub.3)N(CH.sub.2).sub.m N(R.sub.4 R.sub.5 R.sub.6)].sup.2+

where R₁ to R₆, which may be the same or different, can be hydrogen,alkyl or hydroxyalkyl groups containing from 1 to 8 carbon atoms, and upto five of the groups can be hydrogen, and m is in the range 3 to 14.For example zeolite EU-1 (EP 42226), zeolite EU-2 (GB 2 077 709) andzeolite ZSM-23 (EP 125 078, GB 2 202 838) have been prepared using suchtemplates. The use of these templates in the preparation of zeolites andmolecular sieves has also been described in the PhD thesis of J L Cascientitled "The Use of Organic Cations in Zeolite Synthesis" (1982) TheUniversity of Edinburgh, and in the following papers: G W Dodwell, R PDenkewicz and L B Sand "Zeolites", 1985, vol 5, page 153 and J L CasciProc. VII Int. Zeolite Conf., Elsevier, 1986, page 215.

In the method according to the present invention Q is preferably apolymethylene alpha, omega-diammonium cation having the formula:

    [(R.sub.1 R.sub.2 R.sub.3)N(CH.sub.2).sub.m N(R.sub.4 R.sub.5 R.sub.6)].sup.2+

or an amine degradation product thereof, or a precursor thereof where

R₁, R₂, R₃, R₄, R₅ and R₆ may be the same or different and are C₁ to C₃alkyl and m is in the range of 7 to 14

Q is more preferably

    [(CH.sub.3).sub.3 N(CH.sub.2).sub.m N(CH.sub.3).sub.3 ].sup.2+

where m is in the range 8 to 12, and is most preferably

    [(CH.sub.3).sub.3 N(CH.sub.2).sub.10 N(CH.sub.3).sub.3 ].sup.2+

and M and/or Q can be added as hydroxides or salts of inorganic acidsprovided the (R_(1/n))OH/XO₂ ratio is fulfilled.

Suitable precursors of the nitrogen-containing organic cation Q includethe parent diamine with a suitable alkyl halide or the parentdihaloalkane with a suitable trialkylamine. Such materials can be usedas simple mixtures or they can be pre-heated together in the reactionvessel, preferably in solution, prior to the addition of the otherreactants required for the synthesis of zeolite NU-87.

The preferred cation M is an alkali metal especially sodium, thepreferred XO₂ is silica (SiO₂) and the preferred oxide Y₂ O₃ is alumina(Al₂ O₃).

The silica source can be any of those commonly considered for use insynthesising zeolites, for example powdered solid silica, silicic acid,colloidal silica or dissolved silica. Among the powdered silicas usableare precipitated silicas, especially those made by precipitation from analkali metal silicate solution, such as the type known as "KS 300" madeby AKZO, and similar products, aerosil silicas, fumed silicas e.g."CAB-O-SIL" and silica gels suitably in grades for use in reinforcingpigments for rubber and silicone rubber. Colloidal silicas of variousparticle sizes may be used, for example 10-15 or 40-50 microns, as soldunder the Registered Trade Marks "LUDOX", "NALCOAG" and "SYTON". Theusable dissolved silicas include commercially available waterglasssilicates containing 0.5 to 6.0, especially 2.0 to 4.0 mols of SiO₂ permol of alkali metal oxide, "active" alkali metal silicates as defined inUK Patent 1193254, and silicates made by dissolving silica in alkalimetal hydroxide or quaternary ammonium hydroxide or a mixture thereof.

The optional alumina source is most conveniently sodium aluminate, oraluminium, an aluminium salt, for example the chloride, nitrate orsulphate, an aluminium alkoxide or alumina itself, which shouldpreferably be in a hydrated or hydratable form such as colloidalalumina, pseudoboehmite, boehmite, gamma alumina or the alpha or betatrihydrate. Mixtures of the above can be used.

Optionally all or some of the alumina and silica source may be added inthe form of an aluminosilicate.

The reaction mixture is usually reacted under autogenous pressure,optionally with added gas, e.g. nitrogen, at a temperature between 85°C. and 250° C., preferably 120° C. and 200° C., until crystals ofzeolite NU-87 form, which can be from 1 hour to many months depending onthe reactant composition and the operating temperature. Agitation isoptional, but is preferable since it reduces the reaction time and canimprove product purity.

The use of seed material can be advantageous in decreasing the time tonucleation and/or overall crystallisation time. It may also be anadvantage in encouraging the formation of NU-87 at the expense of animpurity phase. Such seed materials include zeolites, especiallycrystals of zeolite NU-87. The seed crystals are usually added in anamount of between 0.01 and 10% of the weight of silica used in thereaction mixture. The use of a seed is particularly desirable when thenitrogen-containing organic cation is a polymethylene alpha,omega-diammonium cation with seven, eight or nine methylene groups i.e.m is 7, 8 or 9.

At the end of the reaction, the solid phase is collected in a filter andwashed, and is then ready for further steps such as drying, dehydrationand ion exchange.

If the product of the reaction contains alkali metal ions, these have tobe at least partly removed in order to prepare the hydrogen form ofNU-87 and this can be done by ion-exchange with an acid, especially amineral acid such as hydrochloric acid or by way of the ammoniumcompound, made by ion exchange with a solution of an ammonium salt suchas ammonium chloride. Ion exchange may be carried out by slurrying onceor several times with the ion exchange solution. The zeolite is usuallycalcined before ion exchange to remove any occluded organic matter sincethis usually facilitates ion exchange.

In general, the cation(s) of zeolite NU-87 can be replaced by anycation(s) of metals, and particularly those in groups 1A, 1B, IIA, IIB,IIIA and IIIB (including rare earths) VIII (including noble metals)other transition metals and by tin, lead and bismuth. (The PeriodicTable is as in "Abridgements of Specifications" published by the UKPatent Office). Exchange is normally carried out using a solutioncontaining a salt of the appropriate cation.

Methods for preparing NU-87 are illustrated by the following Examples.

EXAMPLE 1 Preparation of NU-87

A reaction mixture of molar composition:

    60 SiO.sub.2 --1.333 Al.sub.2 O.sub.3 --10 Na.sub.2 O--7.5 DecBr.sub.2 --3500 H.sub.2 O

was prepared from:

120.2 g "SYTON" X30 (Monsanto: 30% silica sol)

6.206 g "SOAL" 235 (Kaiser Chemicals: molar composition 1.59 Na₂ O --1.0Al₂ O₃ --14.7 H₂ O.

6.30 g Sodium Hydroxide (Analar)

31.4 g DecBr₂

541.5 g Water (deionised)

where DecBr₂ is Decamethonium Bromide:

    [(CH.sub.3).sub.3 N(CH.sub.2).sub.10 N(CH.sub.3).sub.3 ]Br.sub.2

The molar composition given above does not include sodium present in the"SYTON".

The mixture was prepared as follows:

A--solution containing the sodium hydroxide and "SOAL" 235 in 200 g ofwater

B--solution containing the DecBr₂ in 200 g of water

C--141.5 g of water

Solution A was added to the "SYTON" X30, with stirring, over a 30 secondperiod. Mixing was continued for 5 minutes then solution B was added,with stirring, over a 30 second period. Finally, the remaining water, C,was added over a 30 second period. The resulting gel was mixed for afurther 5 minutes before being transferred to a 1 liter stainless steelautoclave.

The mixture was reacted at 180° C., with stirring at 300 rpm using apitched-paddle type impeller.

About 9 days into the reaction the heating and stirring were stopped forabout 2.5 hours before the preparation was restarted.

After a total of 406 hours, at reaction temperature, the preparation wascrash cooled to ambient and the product discharged, filtered, washedwith deionised water and dried at 110° C.

Analysis for Si, Al and Na by atomic adsorption spectroscopy (AAS) gavethe following molar composition:

    37.6 SiO.sub.2 --1.0 Al.sub.2 O.sub.3 --0.14 Na.sub.2 O

Analysis by X-ray powder diffraction showed this as-prepared material tobe highly crystalline sample of NU-87 with the pattern shown in Table 4and FIG. 1.

EXAMPLE 2 Preparation of Hydrogen NU-87

A portion of the material from Example 1 was calcined, in air, at 450°C. for 24 hours followed by 16 hours at 550° C. The material was thenion exchanged for 4 hours with a 1 molar solution of ammonium chloride,at room temperature, using 10 ml of solution per gram of zeolite. Aftertwo such exchanges the resulting NH₄ -NU-87 was then calcined at 550° C.for 16 hours to generate the hydrogen form, that is, H-NU-87.

Analysis by AAS for Si, Al and Na gave the following molar composition:

    36.8 SiO.sub.2 --1.0 Al.sub.2 O.sub.3 --less than 0.001Na.sub.2 O

Analysis by powder X-ray diffraction showed the material to be a highlycrystalline sample of H-NU-87. The diffraction pattern can be seen inFIG. 2 and Table 5.

EXAMPLE 3

A reaction mixture of a molar composition:

    60 SiO.sub.2 --1.5 Al.sub.2 O.sub.3 --10 Na.sub.2 O --7.5 DecBr.sub.2 --3000 H.sub.2 O

was prepared from:

36.1 g "CAB-O-SIL" (BDH Ltd)

6.982 g "SOAL" 235 (Kaiser Chemicals: molar composition 1.59 Na₂ O --1.0Al₂ O₃ --14.7 H₂ O)

6.09 g Sodium Hydroxide (Analar)

31.4 g DecBr₂

535.2 g Water (deionised)

where DecBr₂ is Decamethonium Bromide:

    [(CH.sub.3).sub.3 N(CH.sub.2).sub.10 N(CH.sub.3).sub.3 ]Br.sub.2

The mixture was prepared by the following procedure:

The required amount of water was weighed out. About one third was usedto prepare a solution (solution A) containing the sodium hydroxide and"SOAL" 235. Solution B was prepared containing the Decamethonium Bromidein about one third of the total water. The remaining water was then usedto prepare a dispersion of the silica, "CAB-O-SIL."

Solutions A and B were mixed then added, with stirring, to thedispersion of the "CAB-O-SIL" in water. The resulting mixture was thenreacted in a 1 liter stainless steel autoclave at 180° C. The mixturewas stirred at 300 rpm using a pitched paddle type impeller.

After 258 hours at temperature the preparation was terminated, crashcooled, and discharged. The solid was separated by filtration, washedwith deionised water and dried at 110° C.

Analysis for Na, Si and Al by AAS revealed the following molarcomposition:

    27.5 SiO.sub.2 --1.0 Al.sub.2 O.sub.3 --0.20 Na.sub.2 O

Analysis by X-ray powder diffraction gave the pattern shown in Table 6and FIG. 3. The product was identified as a highly crystalline sample ofNU-87 containing approximately 5% of an analcime impurity.

EXAMPLE 4

A portion of the product from Example 3 was treated with a molarsolution of hydrochloric acid using 50 ml of acid per gram of material.The treatment was carried out at 90° C. for 18 hours after which thesolid was removed by filtration, washed with deionised water and driedat 110° C. After two such treatments the product was examined by powderX-ray diffraction and found to be a highly crystalline sample of NU-87containing no detectable amounts of analcime. The X-ray diffractionpattern can be seen in Table 7 and FIG. 4.

Analysis for Na, Si and Al by AAS revealed the following molarcomposition:

    41.8 SiO.sub.2 --1.0 Al.sub.2 O.sub.3 --0.04 Na.sub.2 O

EXAMPLE 5

The product from Example 3 was calcined in air for 24 hours at 450° C.followed by 16 hours at 550° C. The resulting material was then ionexchanged, for 4 hours at 60° C. with a 1 molar solution of ammoniumchloride using 10 ml of solution per gram of solid calcined product.After ion exchange the material was filtered, washed and dried. Thisprocess was repeated. The material was then calcined at 550° C. for 16hours to generate an H-NU-87 containing approximately 5% of an analcimeimpurity, as determined by powder X-ray diffraction. The actual X-raydata are given in Table 8 and FIG. 5.

Analysis for Na, Si and Al by AAS revealed the following molarcomposition:

    30.7 SiO.sub.2 --1.0 Al.sub.2 O.sub.3 --0.08 Na.sub.2 O

EXAMPLE 6

A portion of the product from Example 4 was calcined and ion-exchangedby the same technique as in Example 5. After calcination the materialwas examined by powder X-ray diffraction and found to be highlycrystalline sample of H-NU-87 containing no detectable impurities. Theactual pattern can be seen in Table 9 and FIG. 6.

Analysis for Na, Si and Al by AAS showed the material to have thefollowing molar composition:

    45.2 SiO.sub.2 --1.0 Al.sub.2 O.sub.3 --0.003 Na.sub.2 O

EXAMPLE 7

Sorption measurements were carried out on a portion of the product fromExample 6. The technique was described above and the results can be seenin Table 3.

EXAMPLE 8

A reaction mixture of molar composition:

    60 SiO.sub.2 --1.5 Al.sub.2 O.sub.3 --9 Na.sub.2 O--2 NaBr--7.5 DecBr.sub.2 --3000 H.sub.2 O

was prepared from:

120.2 g "SYTON" X30 (Monsanto: 30% Silica sol)

6.118 g "SOAL" 235 (Kaiser Chemicals: molar composition 1.40 Na₂ O--Al₂O₃ --12.2 H₂ O)

5.52 g Sodium Hydroxide (Analar)

31.4 g DecBr₂

2.06 g Sodium Bromide

451.9 g Water (deionised)

The molar composition given above does not include sodium present in the"SYTON". The reaction mixture was prepared in a manner similar toExample 1 except that the sodium bromide was added to the sodiumhydroxide, "SOAL" 235 and water to form solution A.

The mixture was reacted in a 1 liter stainless steel autoclave at 180°C., with stirring at 300 rpm using a pitched-paddle type agitator.

After 451 hours at reaction temperature the preparation was terminatedand crash cooled. The product was discharged, filtered, washed withdeionised water and then dried at 110° C.

Analysis by powder X-ray diffraction revealed the product to be asubstantially pure highly crystalline sample of zeolite NU-87 containingno detectable crystalline impurities. The diffraction pattern is givenin FIG. 7 and the interplanar spacings and intensities in Table 10.

Analysis by AAS for Na, Si and Al showed the product to have thefollowing molar composition:

    35.5 SiO.sub.2 --Al.sub.2 O.sub.3 --0.07 Na.sub.2 O

EXAMPLE 9

A reaction mixture of molar composition:

    60 SiO.sub.2 --1.5 Al.sub.2 O.sub.3 --10 Na.sub.2 O--7.5 DecBr.sub.2 --3000 H.sub.2 O

was prepared from:

120.2 g "SYTON" X30 (Monsanto: 30% Silica sol)

6.118 g "SOAL" 235 (Kaiser Chemicals: molar composition-1.40 Na₂ O--Al₂O₃ --12.2 H₂ O)

6.32 g Sodium Hydroxide (Analar)

31.4 g DecBr₂

451.7 g Water (deionised)

The molar composition given above does not include sodium present in the"SYTON".

The mixture was prepared as follows:

A--solution containing the sodium hydroxide and "SOAL" 235 in 200 g ofwater

B--solution containing the DecBr₂ in 200 g of water

C--51.7 g of water

Solution A was added to the "SYTON" X30, with stirring, over a 30 secondperiod. Mixing was continued for 5 minutes then solution B was added,with stirring, over a 30 second period. Finally, the remaining water, C,was added over a 30 second period. The resulting gel was mixed for afurther 5 minutes before being transferred to a 1 liter stainless steelautoclave.

The mixture was reacted at 180° C., with stirring at 300 rpm using apitched-paddle type impeller. Samples were withdrawn at intervals sothat progress of the reaction could be monitored. After a total of 359hours, at reaction temperature, the preparation was crash cooled toambient temperature and the product discharged, filtered, washed withdeionised water and dried at 110° C.

Analysis by X-ray powder diffraction showed the material to beapproximately 80% NU-87 with other crystalline impurities.

Examination of the samples withdrawn from the reaction mixture duringprogress of the reaction by the pH method described in a paper by J LCasci and B M Lowe in Zeolites, 1983, vol 3, page 186 revealed that themain crystallisation event had occurred, by which we mean a majorproportion of the reaction mixture i.e. at least 50.5% crystallised,between a reaction time of 308 and 332 hours.

EXAMPLE 10

Example 9 was repeated except that 1.44 g of NU-87 seed was stirred intothe gel before it was transferred to the stainless steel autoclave.

The mixture was reacted at 180° C., with stirring at 300 rpm using apitched-paddle type impeller. Samples were withdrawn, at intervals, sothat progress of the reaction could be monitored.

After a total of 282 hours at reaction temperature the preparation wascrash cooled to ambient temperature and the product discharged,filtered, washed with deionised water and dried at 110° C.

Analysis for Na, Al and Si by AAS revealed the following molarcomposition:

    35.4 SiO.sub.2 --1.0 Al.sub.2 O.sub.3 --0.09 Na.sub.2 O

Analysis by X-ray powder diffraction showed the material to be a highlycrystalline sample of NU-87 containing approximately 5% of a mordeniteimpurity.

Examination of the samples withdrawn from the reaction mixture duringprogress of the reaction by the pH method referred to in Example 9revealed that the main crystallisation event had occurred between areaction time of 140 and 168 hours.

A comparison of Examples 9 and 10 demonstrate that the use of a seedcrystal:

(a) reduces the total reaction time required to prepare zeolite NU-87and

(b) increases the purity of NU-87 resulting from a particular reactionmixture.

EXAMPLE 11

The product from Example 10 was calcined in air for 24 hours at 450° C.followed by 16 hours at 550° C. The resulting material was then ionexchanged for 4 hours at 60° C. with a 1 molar solution of ammoniumchloride using 10 ml of solution per gram of solid calcined product.After ion exchange the material was filtered, washed and dried. Aftertwo such treatments the resulting NH₄ -NU-87 material was calcined at550° C. for 16 hours to generate an H-NU-87.

Analysis for Na, Al, and Si by AAS revealed the following molarcomposition:

    39.0 SiO.sub.2 --1.0 Al.sub.2 O.sub.3 --less than 0.002 Na.sub.2 O

EXAMPLE 12

A reaction mixture of molar composition:

    60 SiO.sub.2 --1.5 Al.sub.2 O.sub.3 --9 Na.sub.2 O--7.5 DecBr.sub.2 --2 NaBr--3000 H.sub.2 O

was prepared from:

300.4 g "SYTON" X30 (Monsanto: 30% silica sol)

15.29 g "SOAL" 235 (Kaiser Chemicals: molar composition 1.40 Na₂ O--Al₂O₃ --12.2 H₂ O)

13.79 g Sodium Hydroxide (Analar)

78.4 g Decamethonium Bromide (Fluka)

5.15 g Sodium Bromide

1129.6 g Water (deionised)

The molar composition given above does not include sodium present in the"SYTON".

The mixture was prepared as follows:

A--solution containing the sodium hydroxide and "SOAL" 235 in 500 g ofwater

B--solution containing the DecBr₂ in 500 g of water

C--129.6 g of water.

The reaction mixture was prepared in a manner similar to Example 1. Themixture was reacted in a 2 liter stainless steel autoclave at 180° C.,with stirring at 300 rpm using two agitators. The lower part of themixture was stirred using a pitched-paddle type agitator whereas theupper part of the mixture was stirred using a 6-blade turbine typeagitator.

After 408 hours at reaction temperature the preparation was terminatedby crash cooling. The product was discharged, filtered, washed withdeionised water and then dried at 110° C.

Analysis by powder X-ray diffraction showed the material to be a highlycrystalline sample of zeolite NU-87 containing no detactable crystallineimpurities.

EXAMPLE 13

A portion of the material from Example 12 was calcined in air at 450° C.for 24 hours followed by 16 hours at 550° C. The material was thenion-exchanged for 4 hours with a 1 molar solution of ammonium chloride,at 60° C., using 10 ml of solution per gram of solid calcined product.The material was then filtered, washed with deionised water and dried at110° C. After two such exchanges the resulting NH₄ -NU-87 was calcinedat 550° C. for 16 hours to generate the hydrogen form, that is, H-NU-87.Analysis by AAS for Si, Al and Na gave the following molar composition:

    37.9 SiO.sub.2 --1.0 Al.sub.2 O.sub.3 --less than 0.002 Na.sub.2 O

EXAMPLE 14

A reaction mixture of molar composition:

    60 SiO.sub.2 --1.5 Al.sub.2 O.sub.3 --9 Na.sub.2 O--7.5 DecBr.sub.2 --2 NaBr--3000 H.sub.2 O

was prepared from:

2.403 kg "SYTON" X30 (Monsanto: 30% silica sol)

0.1224 kg "SOAL" 235 (Kaiser Chemicals; molar composition 1.40 Na₂O--Al₂ O₃ --12.2 H₂ O)

0.1103 kg Sodium Hydroxide (Analar)

0.6275 kg Decamethonium Bromide

0.0412 kg Sodium Bromide

0.0288 kg NU-87 seed crystals, the product from Example 12

9.0363 kg Water

The molar composition given above does not include the seed crystals orsodium present in the "SYTON".

The mixture was prepared as follows:

A--solution containing the sodium hydroxide, sodium bromide and "SOAL"235 in about one third of the total water

B--solution containing the DecBr₂ in about one third of the total water

C--remaining water

The seed crystals were ground to a fine powder and then stirred into the"SYTON" X30. The mixture was transferred to a 19 liter stainless steelautoclave. The mixture was stirred at ambient temperature and a smallamount of solution C added. To this mixture solution A was addedfollowed by a small amount of solution C. Solution B was then addedfollowed by the remainder of solution C. The autoclave was sealed andthe mixture reacted at 180° C. with stirring and agitation.

After a total of 257 hours at reaction temperature the preparation wasterminated, crash cooled and discharged. The product was separated byfiltration, washed with water and dried at 110° C. This was labelledproduct A. It was noted that a small amount of a granular material(product B) remained in the discharge vessel.

Analysis of product A by powder X-ray diffraction revealed the productto be a highly crystalline sample of zeolite NU-87 containingapproximately 5% of a crystalline impurity.

EXAMPLE 15

A portion of product A from Example 14 was calcined, in air, at 450° C.for 24 hours followed by 16 hours at 550° C. The resulting material wasthen contacted for 4 hours at 60° C. with a 1 molar solution of ammoniumchloride using 10 ml of solution per gram of solid calcined product.After ion exchange the material was filtered, washed with deionisedwater and then dried at 110° C. After two such treatments the resultingNH₄ -NU-87 was calcined at 550° C. for 16 hours to generate H-NU-87.

Analysis for Na, Al and Si by AAS gave the following molar composition:

    37 SiO.sub.2 --Al.sub.2 O.sub.3 --0.004 Na.sub.2 O

EXAMPLE 16

The procedure of Example 15 was repeated using a fresh portion ofproduct A from Example 14.

Analysis, by AAS, for Na, Si and Al gave the following molarcomposition:

    37.0 SiO.sub.2 --Al.sub.2 O.sub.3 --0.002 Na.sub.2 O

                  TABLE 4                                                         ______________________________________                                        X-RAY DATA FOR THE PRODUCT OF EXAMPLE 1                                       d (Angstroms) Relative Intensity (I/Io)                                       ______________________________________                                        12.53         7                                                               11.11         53                                                              10.56         23                                                              9.01          3                                                               8.34          7                                                               6.83          5                                                               6.54          4                                                               5.56          4                                                               5.47          5                                                               5.30          4                                                               5.15          3                                                               5.02          3                                                               4.62          42                                                              4.52          7                                                               4.40          38                                                              4.32          100                                                             4.17          22                                                              3.99          78                                                              3.93          43                                                              3.85          21                                                              3.84          20                                                              3.71          40                                                              3.60          10                                                              3.44          36                                                              3.42          40                                                              3.38          25                                                              3.35          22                                                              3.27          58                                                              3.24          34                                                              3.16          15                                                              3.08          11                                                              3.01          6                                                               2.90          13                                                              2.86          7                                                               2.74          3                                                               2.72          4                                                               2.69          3                                                               2.64          3                                                               2.59          4                                                               2.55          8                                                               2.52          21                                                              2.46          9                                                               2.45          8                                                               2.40          13                                                              2.39          12                                                              2.32          9                                                               2.29          5                                                               2.19          4                                                               2.11          8                                                               2.10          8                                                               2.04          5                                                               2.01          12                                                              1.99          12                                                              ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        X-RAY DATA FOR THE PRODUCT OF EXAMPLE 2                                       d (Angstroms) Relative Intensity (I/Io)                                       ______________________________________                                        12.40         14                                                              11.06         100                                                             10.47         41                                                              9.94           4                                                              9.00           7                                                              8.30          12                                                              6.79          19                                                              6.51           4                                                              6.31           6                                                              5.44           8                                                              4.59          56                                                              4.49           8                                                              4.38          36                                                              4.31          89                                                              4.16          23                                                              3.97          87                                                              3.90          48                                                              3.84          23                                                              3.73          37                                                              3.71          42                                                              3.60          13                                                              3.55          11                                                              3.41          46                                                              3.37          33                                                              3.33          32                                                              3.26          93                                                              3.23          43                                                              3.16          20                                                              3.08          18                                                              3.00           7                                                              2.98           8                                                              2.89          17                                                              2.79           3                                                              2.73           7                                                              2.68           3                                                              2.65           5                                                              2.64           5                                                              2.55          10                                                              2.51          24                                                              2.45          11                                                              2.39          19                                                              2.38          16                                                              2.32          10                                                              2.29           5                                                              2.20           4                                                              2.11           5                                                              2.09           7                                                              2.03           7                                                              2.01          13                                                              2.00          13                                                              ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        X-RAY DATA FOR THE PRODUCT OF EXAMPLE 3                                       d (Angstroms) Relative Intensity (I/Io)                                       ______________________________________                                        12.62          8                                                              11.14         51                                                              10.59         23                                                              8.35           7                                                              6.84           4                                                              6.54           3                                                              5.57          13                                                              5.48           5                                                              5.29           4                                                              5.03           4                                                              4.63          42                                                              4.40          39                                                              4.32          100                                                             4.17          22                                                              3.99          78                                                              3.93          47                                                              3.84          17                                                              3.71          37                                                              3.60          13                                                              3.45          31                                                              3.42          55                                                              3.38          32                                                              3.35          26                                                              3.27          63                                                              3.24          36                                                              3.15          18                                                              3.09          14                                                              3.01           9                                                              2.91          24                                                              2.86           9                                                              2.81           6                                                              2.72           7                                                              2.68           8                                                              2.59           8                                                              2.52          24                                                              2.46          13                                                              2.40          17                                                              2.38          14                                                              2.32          13                                                              2.29          13                                                              2.28           6                                                              2.21           7                                                              2.19           9                                                              2.16           7                                                              2.10          15                                                              2.04          11                                                              2.01          16                                                              ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        X-RAY DATA FOR THE PRODUCT OF EXAMPLE 4                                       d (Angstroms) Relative Intensity (I/Io)                                       ______________________________________                                        12.52          6                                                              11.06         49                                                              10.50         21                                                              8.97           5                                                              8.31           6                                                              6.81           4                                                              6.51           3                                                              5.54           5                                                              5.46           4                                                              5.29           4                                                              5.01           3                                                              4.62          35                                                              4.50           6                                                              4.39          37                                                              4.31          100                                                             4.16          21                                                              3.98          69                                                              3.92          43                                                              3.83          17                                                              3.70          40                                                              3.61          11                                                              3.44          22                                                              3.4           41                                                              3.37          30                                                              3.35          24                                                              3.27          60                                                              3.23          33                                                              3.15          18                                                              3.09          12                                                              3.08          13                                                              3.01           8                                                              2.97           6                                                              2.92          12                                                              2.89          15                                                              2.85           9                                                              2.81           5                                                              2.71           6                                                              2.68           5                                                              2.66           5                                                              2.63           5                                                              2.59           7                                                              2.54          11                                                              2.52          21                                                              2.46          12                                                              2.40          15                                                              2.38          13                                                              2.32          11                                                              2.29           8                                                              2.24           4                                                              2.19           7                                                              2.15           6                                                              2.10          13                                                              2.03          10                                                              2.01          13                                                              ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        X-RAY DATA FOR THE PRODUCT OF EXAMPLE 5                                       d (Angstroms) Relative Intensity (I/Io)                                       ______________________________________                                        12.41         17                                                              11.10         96                                                              10.48         42                                                              8.99           4                                                              8.31          13                                                              6.79          21                                                              6.51           4                                                              6.33           5                                                              5.53          10                                                              5.45          10                                                              4.60          61                                                              4.50           7                                                              4.38          43                                                              4.32          88                                                              4.16          26                                                              3.98          87                                                              3.91          52                                                              3.83          17                                                              3.72          42                                                              3.60          17                                                              3.56          14                                                              3.41          57                                                              3.37          40                                                              3.34          38                                                              3.26          100                                                             3.16          24                                                              3.08          22                                                              3.07          20                                                              3.00          11                                                              2.98          11                                                              2.92          17                                                              2.90          25                                                              2.80           7                                                              2.73          10                                                              2.65           9                                                              2.63          10                                                              2.55          14                                                              2.51          31                                                              2.45          17                                                              2.39          24                                                              2.32          14                                                              2.29          11                                                              2.24           7                                                              2.20          10                                                              2.15           8                                                              2.11          11                                                              2.09          13                                                              2.03          13                                                              2.00          18                                                              ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                        X-RAY DATA FOR THE PRODUCT OF EXAMPLE 6                                       d (Angstroms) Relative Intensity (I/Io)                                       ______________________________________                                        12.44         14                                                              11.12         84                                                              10.52         37                                                              9.01           6                                                              8.33          10                                                              6.81          19                                                              6.53           4                                                              6.32           4                                                              5.81           3                                                              5.45           8                                                              4.60          56                                                              4.39          39                                                              4.32          89                                                              4.17          25                                                              3.98          82                                                              3.91          49                                                              3.84          16                                                              3.73          41                                                              3.60          16                                                              3.56          14                                                              3.41          49                                                              3.37          33                                                              3.34          36                                                              3.26          100                                                             3.16          24                                                              3.08          22                                                              3.01          10                                                              2.98           9                                                              2.90          20                                                              2.86          12                                                              2.80           7                                                              2.73           9                                                              2.69           7                                                              2.65           8                                                              2.63           9                                                              2.55          13                                                              2.51          30                                                              2.45          16                                                              2.39          23                                                              2.32          13                                                              2.29          10                                                              2.24           6                                                              2.20           9                                                              2.16           7                                                              2.13           8                                                              2.11          11                                                              2.09          12                                                              2.03          12                                                              2.01          18                                                              2.00          16                                                              ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                        X-RAY DATA FOR THE PRODUCT OF EXAMPLE 8                                       d (Angstroms) Relative Intensity (I/Io)                                       ______________________________________                                        12.46          6                                                              11.05         53                                                              10.50         20                                                              8.29           6                                                              6.82           4                                                              5.58           3                                                              5.47           4                                                              5.28           3                                                              5.02           3                                                              4.62          31                                                              4.39          35                                                              4.31          100                                                             4.16          20                                                              3.98          60                                                              3.92          35                                                              3.85          20                                                              3.82          16                                                              3.71          43                                                              3.59           9                                                              3.49           7                                                              3.42          38                                                              3.38          21                                                              3.34          20                                                              3.26          57                                                              3.23          30                                                              3.16          16                                                              3.15          14                                                              3.09          12                                                              3.07          11                                                              3.01           7                                                              2.98           7                                                              2.91          12                                                              2.90          14                                                              2.86           8                                                              2.71           6                                                              2.68           5                                                              2.64           5                                                              2.59           6                                                              2.54          10                                                              2.52          16                                                              2.46          10                                                              2.40          14                                                              2.38          14                                                              2.32          11                                                              2.29           7                                                              2.24           4                                                              2.19           7                                                              2.16           5                                                              2.10          10                                                              2.07           4                                                              2.04           7                                                              2.01          12                                                              2.00          14                                                              1.99          11                                                              ______________________________________                                    

In the catalysts according to the invention XO₂ is preferably silica andY₂ O₃ is preferably alumina. Such catalysts may be used in a widevariety of catalytic processes and using a wide variety of feedstocks.

Catalytically useful forms of zeolite NU-87 include the hydrogen andammonium forms, prepared by the methods hereinbefore described.

Catalysts according to the invention comprising NU-87 may also compriseone or more elements, especially metals or cations thereof, or compoundsof said elements, especially metal oxides. Such catalysts may beprepared by ion-exchange or impregnation of zeolite NU-87 with the saidelement, cation or compound, or a suitable precursor of said cation orcompound. Such ion-exchange or impregnation may be carried out on theas-prepared zeolite NU-87, the calcined form, the hydrogen form and/orthe ammonium form and/or any other exchanged form.

In cases where a metal-containing form of zeolite NU-87 is prepared byion-exchange it may be desirable to effect complete exchange of themetal, by which is meant that substantially all of the exchangeablesites are occupied by the metal. In most cases, however, it ispreferable to effect only partial exchange of the metal, the remainingsites being occupied by another cation especially hydrogen or ammoniumcations. In some cases it may be desirable to introduce two or moremetal cations by ion exchange.

In cases where zeolite NU-87 is impregnated with a metal compound toform a catalyst, the metal compound may be added in any suitablequantity, but 20% by weight is generally sufficient for mostapplications; for some applications up to 10% by weight is sufficient,and quantities of up to 5% are often appropriate. Impregnation may becarried out by any suitable method known in the art of catalystpreparation.

Metal-exchanged forms or forms in which a metal compound has beenimpregnated may be used as such or they may be treated to produce anactive derivative. Treatments include reduction, for example in anatmosphere comprising hydrogen, to produce a metal or other reducedforms. Such treatments may be carried out at a suitable stage in thecatalyst preparation or may conveniently be carried out in the catalyticreactor.

Catalytic compositions comprising zeolite NU-87 can, if desired, beassociated with an inorganic matrix which may be either inert orcatalytically active. The matrix may be present solely as a bindingagent to hold the zeolite particles together, possibly in a particularshape or form, for example as a pellet or extrudate, or it may functionas an inert diluent, for example to control the activity per unit weightof catalyst. When the inorganic matrix or diluent is itselfcatalytically active it can thereby form an effective part of thezeolite/matrix catalyst composition. Suitable inorganic matrices anddiluents include conventional catalyst support materials such as silica,the various forms of alumina, clays such as bentonites,montmorillonites, sepiolite, attapulgite, Fullers Earth and syntheticporous materials such as silica-alumina, silica-zirconia, silica-thoria,silica-beryllia or silica-titania. Combinations of matrices arecontemplated within the present invention, especially combinations ofinert and catalytically-active matrices.

When zeolite NU-87 is associated with an inorganic matrix material or aplurality thereof, the proportion of matrix material or materials in thetotal composition usually amounts to up to about 90% by weight,preferably up to 50% by weight, more preferably up to 30% by weight.

For some applications another zeolite or molecular sieve may be used inconjunction with zeolite NU-87 to form a catalyst. Such a combinationmay be used as such or associated with one or more matrix materialshereinbefore described. A particular example of the use of such anoverall composition is as a fluid catalytic cracking catalyst additive,in which case zeolite NU-87 is preferably used in an amount of 0.5 to 5%by weight of the total catalyst.

For other applications zeolite NU-87 may be combined with anothercatalyst, such as platinum on alumina.

Any convenient method of mixing zeolite NU-87 with an inorganic matrixand/or another zeolite material, may be employed, especially that suitedto the final form in which the catalyst is used, for example extrudates,pellets or granules.

If zeolite NU-87 is used to form a catalyst in conjunction with a metalcomponent (for example, a hydrogenation/dehydrogenation component orother catalytically active metal) in addition to an inorganic matrix,the metal component can be exchanged or impregnated into the zeoliteNU-87 itself before addition of the matrix material or into thezeolite-matrix composition. For some applications it may be advantageousto add the metal component to the whole or part of the matrix materialbefore mixing the latter with the zeolite NU-87.

A wide range of hydrocarbon conversion catalysts comprising zeoliteNU-87 can be prepared by ion-exchange or impregnation of the zeolitewith one or more cations or oxides derived from elements selected fromCu, Ag, Ga, Mg, Ca, Sr, Zn, Cd, B, Al, Sn, Pb, V, P, Sb, Cr, Mo, W, Mn,Re, Fe, Co, Ni and noble metals.

In cases where catalysts comprising zeolite NU-87 contain one or morehydrogenation/dehydrogenation components such as the metals Ni, Co, Pt,Pd, Re and Rh, such components can be introduced by ion-exchange orimpregnation of a suitable compound of the metal.

Catalyst compositions comprising zeolite Nu-87 may find application inreactions involving saturated and unsaturated aliphatic hydrocarbons,aromatic hydrocarbons, oxygenated organic compounds and organiccompounds containing nitrogen and/or sulphur as well as organiccompounds containing other functional groups.

In general, catalyst compositions comprising zeolite NU-87 can beusefully employed in reactions involving isomerisation, transalkylationand disproportionation, alkylation and de-alkylation, dehydration andhydration, oligomerisation and polymerisation, cyclisation,aromatisation, cracking, hydrogenation and dehydrogenation, oxidation,halogenation, synthesis of amines, hydrodesulphurisation andhydrodenitrification, ether formation and synthesis of organic compoundsin general.

The above processes may be carried out in either the liquid or vapourphase under conditions which are chosen as suitable for each individualreaction. For example, the reactions carried out in the vapour phase mayinvolve the use of fluid bed, fixed bed or moving bed operations.Process diluents may be used when required. Depending upon theparticular process, suitable diluents include inert gases (such asnitrogen or helium), hydrocarbons, carbon dioxide, water or hydrogen.The diluent may be inert or it may exert a chemical effect. It may be anadvantage, especially in cases where hydrogen is used, to include ametal component, such as a hydrogenation/dehydrogenation component, forexample one or more of the metals, Ni, Co, Pt, Pd, Re or Rh as part ofthe catalyst composition.

According to a further aspect of the present invention we provide ahydrocarbon conversion process which comprises contacting analkylbenzene or a mixture of alkylbenzenes under isomerisationconditions in the vapour or liquid phase with a catalyst comprisingzeolite NU-87.

Isomerisation reactions for which catalysts comprising zeolite NU-87 areof particular use are those involving alkanes and substituted aromaticmolecules, especially xylenes. Such reactions may include those whichcan be carried out in the presence of hydrogen. Catalyst compositionscontaining zeolite NU-87 which are of particular use in isomerisationreactions include those in which the NU-87 is in its acid (H) form,cation-exchanged form, or other metal-containing forms or combinationsthereof. Especially useful are those forms in which the metal is ahydrogenation/dehydrogenation component such as Ni, Co, Pt, Pd, Re orRh.

Particular isomerisation reactions in which a catalyst comprising NU-87may be found useful include xylene isomerisation and hydroisomerisationof xylenes, paraffin, in particular C₄ to C₁₀ normal hydrocarbons, orolefin isomerisation and catalytic dewaxing.

Xylene isomerisation and hydroisomerisation may be carried out in theliquid or vapour phase. In the liquid phase, suitable isomerisationconditions include a temperature in the range 0°-350° C., a pressure inthe range 1-200 atmospheres absolute, preferably 5-70 atmospheresabsolute, and when conducted in a flow system, a weight hourly spacevelocity (WHSV) preferably in the range 1-30 hr⁻¹ based on the totalcatalyst composition. Optionally, a diluent may be present, suitably oneor more of those having a critical temperature higher than theisomerisation conditions being used. The diluent, if present, maycomprise 1-90% by weight of the feed. Vapour phase xylene isomerisationand hydroisomerisation reactions are most suitably carried out at atemperature in the range 100°-600° C., preferably 200°-500° C., at apressure in the range 0.5-100 atmosphere absolute, preferably 1-50atmospheres absolute, and at a WHSV up to 80 based on the total catalystcomposition.

When xylene isomerisation is conducted in the presence of hydrogen (inthe vapour phase), the preferred hydrogenation/dehydrogenation componentis Pt or Ni. The hydrogenation/dehydrogenation component is usuallyadded in an amount of between 0.05 and 2% by weight of the totalcatalyst. Additional metals and/or metal oxides may be present in thecatalyst composition.

In xylene isomerisation, ethylbenzene may be present in the xylene feedin amounts up to 40% by weight. Over catalyst compositions comprisingzeolite NU-87 the ethylbenzene will undergo transalkylation with itself,and with xylenes, to form heavier and lighter aromatic compounds. Theethylbenzene will also react to form benzene and light gas, particularlyat temperatures above 400° C. With such xylene feeds containingethylbenzene, when reaction is carried out in the presence of hydrogenover a catalyst composition comprising zeolite NU-87 together with ahydrogenation/dehydrogenation component, some of the ethylbenzene willisomerise to xylenes. It may also be an advantage to carry out xyleneisomerisation reactions in the presence of a hydrocarbon compound,especially a paraffin or naphthene with or without the additionalpresence of hydrogen. The hydrocarbon appears to improve catalystperformance in that reactions which lead to xylenes loss are suppressedand, particularly when reactions are carried out in the absence ofhydrogen, catalyst life is extended.

According to yet a further aspect of the present invention we provide ahydrocarbon conversion process which comprises contacting one or morealkylated aromatic compounds under transalkylation conditions in thevapour or liquid phase with a catalyst comprising zeolite NU-87.

Catalysts comprising zeolite NU-87 are of especial value intransalkylation and disproportionation reactions, in particular thosereactions involving mono-, di-, tri- and tetra-alkyl substitutedaromatic molecules, especially toluene and xylenes.

Catalyst compositions comprising NU-87 which are of particular use intransalkylation and disproportionation reaction include those in whichthe NU-87 component is in its acid (H) form, its cation-exchanged form,or other metal-containing forms or combinations thereof. Especiallyuseful is the acid form and those forms in which the metal is ahydrogenation/dehydrogenation component such as Ni, Co, Pt, Pd, Re orRh.

Particular examples of important processes include toluenedisproportionation and the reaction of toluene with aromatic compoundscontaining 9 carbon atoms, for example trimethyl benzenes.

Toluene disproportionation can be conducted in the vapour phase eitherin the presence or absence of hydrogen, although the presence ofhydrogen is preferred as this helps to suppress catalyst deactivation.The most suitable reaction conditions are: temperatures in the range250°-650° C., preferably 300°-550° C.; pressures in the range 0.3-100atmospheres absolute, preferably 1-50 atmospheres absolute; weighthourly space velocity up to 50 (based on the total catalystcomposition).

When toluene disproportionation is conducted in the presence of hydrogenthe catalyst may, optionally, contain a hydrogenation/dehydrogenationcomponent. The preferred hydrogenation/dehydrogenation component is Pt,Pd, or Ni. The hydrogenation/dehydrogenation component is normally addedin a concentration of up to 5% by weight of the total catalystcomposition. Additional metals and/or metal oxides may be present in thecatalyst composition, for example up to 5% by weight of the totalcatalyst composition.

The present invention further provides a hydrocarbon conversion processwhich comprises reacting an olefinic or aromatic compound with asuitable alkylating compound under alkylating conditions in the vapouror liquid phase over a catalyst comprising zeolite NU-87.

Among the alkylation reactions for which catalysts comprising zeoliteNU-87 are of particular use are the alkylation of benzene or substitutedaromatic molecules with methanol or an olefin or ether. Specificexamples of such processes include toluene methylation, ethylbenzenesynthesis, and the formation of ethyl toluene and cumene. Alkylationcatalysts used in processes according to this further aspect of theinvention may comprise further materials, especially metal oxides whichmay improve catalytic performance.

Catalysts comprising zeolite NU-87 may find application in reactionsinvolving the dehydration of alcohols, for example methanol and higheralcohols, to form hydrocarbons, including olefins and gasoline. Otherfeedstocks for dehydration reactions involving a catalyst comprisingNU-87 include ethers, aldehydes and ketones.

By the use of a catalyst comprising NU-87, hydrocarbons can be generatedby carrying out oligomerisation, cyclisation and/or aromatisationreactions on unsaturated compounds such as ethene, propene butenes, onsaturated compounds such as propane or butane or mixtures ofhydrocarbons such as light napthas. For some reactions, particularlyaromatisation reactions, the catalyst may usefully comprise a metal ormetal oxide, especially platinum, gallium, zinc or their oxides.

Catalysts comprising NU-87 are of use in a variety of crackingreactions, including the cracking of olefins, paraffins or aromatics ormixtures thereof. Of particular value is the use of zeolite NU-87 as afluid catalytic cracking catalyst additive to improve the product of thecracking reaction. Zeolite NU-87 may also be used as a component of acatalyst in catalytic dewaxing or hydrocracking processes.

Hydrogenation/dehydrogenation processes, for example the dehydrogenationof alkanes to the corresponding olefins, are suitably carried out bycontacting the appropriate feedstock under appropriate conditions with acatalyst comprising zeolite NU-87, especially when the latter alsocomprises a hydrogenation/dehydrogenation component such as Ni, Co, Pt,Pd, Re or Ru.

Zeolite NU-87 is useful as a component in a catalyst for the preparationof amines, for example the production of methylamines from methanol andammonia.

Zeolite Nu-87 is also a useful catalyst for the formation of ethers,particularly by the reaction of two alcohols or by the reaction of anolefin with an alcohol, especially the reaction of methanol withisobutene or pentenes.

The invention relating to catalysts comprising NU-87 and processes usingthese catalysts is illustrated by the following Examples.

EXAMPLE 17 Cracking of N-Butane EXAMPLE 17a

The cracking of n-butane over H-NU-87 was examined using a portion ofthe material from Example 5. The procedure followed that described by: HRastelli Jr., BM Lok, J A Duisman, D E Earls and J T Mullhaupt, CanadianJournal of Chemical Engineering, Volume 60, February 1982, pages 44-49.The contents of which are incorporated herein by reference.

A portion of the product from Example 5 was pelleted, broken down andsieved to give a 500-1000 micron size fraction. 0.6293 g of thismaterial, which had been previously dehydrated by heating at 500° C. for4 hours in a stream of dry nitrogen, were charged to a stainless-steelmicro reactor. Before carrying out the reaction the material was heatedfor 18 hours in stream of dry air.

A feed containing 2.1% v/v n-butane, 15.2% v/v nitrogen and 82.7% v/vhelium was passed over the catalyst. The catalyst was maintained at atemperature of 500° C. The cracked products were analysed by gaschromatography. This showed that the zeolite cracked n-butane to C₁ -C₃hydrocarbons. At a feed flow rate of 50 cm³ per minute an n-butaneconversion of 60% was measured which corresponds to a k_(A) of 72.8 cm³/g min using the equation given in the above reference.

EXAMPLE 17b

The cracking of n-butane over H-NU-87 was examined using a portion ofthe material from Example 15. The procedure followed that described inExample 17a.

A portion of the product from Example 15 was pelleted, broken-down andsieved to give a 500-1000 micron size fraction. 0.4006 g of thismaterial was charged to a stainless-steel micro reactor (internaldiameter 4.6 mm) and supported on glass wool and glass balls. Thematerial was then dehydrated "in situ" by heating at 500° C. for 18hours in a stream of dry nitrogen.

A feed containing 2.0 mole % n-butane, 15.2% mole nitrogen and 82.8 mole% helium was passed over the catalyst bed. The catalyst bed wasmaintained at a temperature of 500° C. and atmospheric pressure. Thecracked products were analysed by gas chromatography. At a feed flowrate of 96.8 cm³ per minute an n-butane conversion of 41.7% wasmeasured. This corresponds to a k_(A) of 144.8 cm³ /g min. The feed flowrate was then reduced to 51.7 cm³ per minute and gave an n-butaneconversion of 62.1%. This corresponds to a k_(A) of 139.0 cm³ /g min.

The zeolite cracked the n-butane giving the following products:

    ______________________________________                                        Feed flow   Weight %                                                          rate (cm.sup.3 /min)                                                                      CH.sub.4 C.sub.2 H.sub.6                                                                      C.sub.2 H.sub.4                                                                      C.sub.3 H.sub.8                                                                    C.sub.3 H.sub.6                       ______________________________________                                        96.8        8.9      11.0   23.0   33.5 23.6                                  51.7        9.2      11.1   22.3   39.5 17.9                                  ______________________________________                                    

The zeolite was then regenerated by heating at 500° C. for 25.5 hours ina stream of dry air. The feed was reintroduced at a feed flow rate of96.8 cm³ per minute and a n-butane conversion of 43.3% was measured.This corresponds to a k_(A) of 152.2 cm³ /g min. The feed flow rate wasreduced to 50.7 cm³ per minute and a n-butane conversion of 62.9% wasmeasured. This corresponds to a k_(A) of 139.1 cm³ /g min.

These examples show that zeolite NU-87 is an active catalyst forn-butane cracking.

The following example illustrates the use of zeolite NU-87 inTransalkylation/Disproportionation reactions.

EXAMPLE 18 Disproportionation of Toluene

A portion of the material from Example 5 was pelleted, broken down andsieved to give aggregates of between 425 and 1000 microns. 0.5 g of thismaterial was placed in a 5 mm internal diameter stainless steel reactorand calcined at 500° C. in air for 16 hours at atmospheric pressure. Theair was replaced by nitrogen and the reactor and contents were cooled to350° C. Hydrogen was then passed through the reactor and the pressureraised to 20 bar. The flow rate was set at 2.59 liters per hour asmeasured at atmospheric pressure. After 1 hour, toluene was introducedinto the hydrogen stream at a rate of 2.85 mls of liquid per hour. Themole ratio of hydrogen to toluene was 4 to 1.

The compositions of the product in weight percent at various times aregiven in Table 11. This shows that zeolite NU-87 is highly active andselective catalyst for the disproportionation of toluene.

The following examples illustrate the use of zeolite NU-87 inisomerisation reactions.

EXAMPLE 19 Hhydroisomerisation of N-Pentane EXAMPLE 19a

A slurry consisting of 2.31 g of the material from Example 15, 0.85 mlof a chloroplatinic acid solution and 28 ml of deionised water wasstirred in a closed vessel at room temperature for 4 hours. (Thechloroplatinic acid solution contained the equivalent of 0.368 g ofplatinum in 25 ml of deionised water). Water was then evaporated fromthe mixture using a rotary evaporator and the resultant solid calcinedin air at 500° C. for 3 hours.

The platinum impregnated zeolite powder thus produced was analysed byAtomic Adsorption Spectroscopy (AAS) and found to contain 0.41 weightpercent platinum. The powder was pelleted, broken-down and sieved togive a 500 to 1000 micron size fraction. 1.12 g of this material wastransferred to a stainless steel reactor (internal diameter 4.2 mm) andreduced under a stream of hydrogen at 250° C. and a pressure of 450 psigfor 24 hours. Liquid n-pentane, which had previously been dried over amolecular sieve, was vaporised and mixed with hydrogen gas to produce amixture with a molar ratio of H₂ to pentane of 1.5:1. This mixture waspassed over the catalyst bed at a weight hourly space velocity (WHSV) of1.1 hour⁻¹ based on the n-pentane at a pressure of 450 psig and atemperature of 250° C. The product leaving the reactor bed was analysedby on line chromatography. It was found to contain 72% isopentane and28% n-pentane. This corresponds to a conversion of 72%. This productcomposition is equivalent to the limiting thermodynamic equilibriummixture of n- and iso-pentane at 250° C. Thus, this example demonstratesthe high activity of the Pt-NU-87 catalyst in n-pentanehydroisomerisation.

Example 19b

X--solution of 0.150 g of Pt(NH₃)₄ Cl₂ in 5 ml of deionised wateradjusted to pH 10 using concentrated ammonia solution

Y--solution of 2M NH₄ NO₃ adjusted to pH 10 using concentrated ammoniasolution

Z--dilute ammonia solution of pH 10.

A solution comprising 0.66 ml of X, 5.9 ml of Y and 15 ml of Z wasstirred with 2.62 g of material from Example 15 for 48 hours at 90° C.The zeolite was filtered, washed with dilute ammonia solution (pH 10 andthen calcined in static air as follows:

(a) temperature increasing from 25° to 100° C. over a period of 2 hours;

(b) 100° C. for 3 hours;

(c) temperature increasing from 100° to 395° C. over a period of 6hours;

(d) 395° C. for 2 hours;

(e) temperature increasing from 395° to 550° C. over a period of 4hours; and

(f) 550° C. for 3 hours

The resulting catalyst powder was analysed by AAS and found to contain0.28 weight percent platinum. The powder was pelleted, broken down andsieved to give a 500 to 1000 micron size fraction.

0.98 g of this material was transferred to the reactor described inExample 19a. The material was reduced at a temperature of 251° C. and apressure of 450 psig for 24 hours. Hydrogen and liquid n-pentane, molarratio H₂ to pentane of 1.2:1 was prepared using the method described inExample 19a. Finally the procedure described in Example 19a was used totest the catalyst. The weight hourly space velocity of the n-pentaneover the catalyst bed was 1.0 hour⁻¹. The product contained 67%iso-pentane and 33% n-pentane.

This example demonstrates that a platinum containing form of zeoliteNU-87, prepared either by impregnation or ion exchange, is highly activefor the hydroisomerisation of n-pentane.

EXAMPLE 20 Hydroisomerisation of Xylenes

A portion of the material from Example 5 was pelleted, broken down andsieved to give aggregates of between 425 and 1000 microns. 0.1 g of thismaterial were placed in a 2 mm internal diameter stainless steel tubularreactor and calcined in air for 16 hours at 500° C. The air was purgedwith nitrogen and the reactor and contents were cooled to 400° C.Hydrogen was introduced into the reactor at a flow rate of 4.9 litersper hour, as measured at atmospheric pressure, and the pressure wasincreased to 80 psig. After 1 hour the temperature was reduced to 275°C. A mixture of C₈ aromatic hydrocarbons was added to the hydrogenstream at a rate of 5 ml of liquid per hour. The mole ratio of hydrogento hydrocarbon was 5 to 1. The temperature was raised in steps to 400°C., at which temperature reasonable conversions were obtained. Thetemperature was further increased to 450° C. and then to 480° C.

The feed and product compositions are given in Table 12.

EXAMPLE 21 Low Pressure Isomerisation in the Absence of Hydrogen

A portion of the material from Example 5 was pelleted, broken down andsieved to give aggregates of between 425 and 1000 microns. 0.5 g of theaggregates were placed in a 5 mm internal diameter stainless steeltubular reactor and calcined for 16 hours at 500° C. The air was purgedwith nitrogen and the reactor and contents were cooled to 350° C. and amixture of C₈ aromatics were passed over the catalyst at a rate of 21 mlof liquid per hour. Table 13 gives the feed and product compositionsafter 10 hours on line.

These examples show that zeolite NU-87 can be used to catalyse theisomerisation of xylenes with very little xylenes loss. In addition, theloss of ethylbenzene, desirable for efficient xylene isomerisation plantoperation, was quite high.

The following examples illustrate the use of catalyst compositionscontaining zeolite NU-87 in alkylation reactions.

EXAMPLE 22 Methylation of Toluene in the Presence of Hydrogen

The catalyst material which had been used in Example 20 was recoveredand then calcined in air at 500° C. for 16 hours then cooled to 400° C.in Nitrogen. Hydrogen was passed over the catalyst at 2.5 liters perhour, as measured at atmospheric pressure, and the pressure in thereactor was raised to 20 bar. After 1 hour the temperature was reducedto 323° C. A mixture of toluene and methanol, in the mole ratio of 3 to1 was added to the hydrogen stream at a rate of 2.5 ml liquid per hour.The temperature was raised in steps to 460° C. The compositions of thearomatics in the product are given in Table 14.

EXAMPLE 23 Methylation of Toluene at Atmospheric Pressure in the Absenceof Hydrogen

A portion of the material from Example 5 was pelleted, broken down andsieved to give aggregates of between 425 and 1000 microns. 0.5 g of thismaterial were placed in a 5 mm internal diameter stainless steel tubularreactor and calcined at 500° C. in air at atmospheric pressure for 16hours. The aggregates were cooled in nitrogen to 300° C. A mixture oftoluene and methanol, in the mole ratio of 3 to 1, was pumped throughthe reactor at various flow rates. The composition of the aromatics inthe product at various times can be seen in Table 15.

These Examples illustrate the use of zeolite NU-87 as a catalyst in thealkylation of toluene with methanol, both in the presence and absence ofhydrogen.

EXAMPLE 24 Ethylation of Benzene

A portion of the product from Example 16 was pelleted, broken down andsieved to give a 425-1000 micron size fraction. 1.0 g of this materialwas placed in a stainless steel reactor tube (internal diameter 4 mm)and heated in air at 500° C. for 16 hours. The tube was then purged withnitrogen as it was cooled to 400° C.

Ethylene was passed into the tube and the pressure was allowed to riseto 13.6 bar. The ethylene flow was set at 11.2 ml/min measured atatmospheric pressure and ambient temperature. Benzene was introduced ata liquid rate of 12.5 ml/hr. The rates were then adjusted to 6.3 ml/minof ethylene and 3.2 ml/hr of benzene. The mole ratio of benzene toethylene was then 2.25.

The compositions of the product in weight percent at various times aregiven in Table 16. It is clear from the results that overall selectivityto ethylbenzenes is high. Thus, zeolite NU-87 is a highly selectivecatalyst for the ethylation of benzene.

EXAMPLE 25 Use of NU-87 as an Etherification Catalyst

A portion of the material from Example 15 was pelleted, broken down andsieved to give a 500 to 1000 micron size fraction. 0.75 g of thismaterial was placed in a reactor consisting of 5 stainless steel tubes(internal diameter of 5 mm) in series.

A liquid feed comprising methanol and a mixture containing mainly C₅hydrocarbons of which approximately 21% by weight was 2 MB (2MB=mixtureof 2-methylbutene-1 and 2-methylbutene-2) (mole ratio of 2MB to methanolof 1.0:0.7) was continuously passed through the reactor at various ratesand temperatures as shown below. A pressure of 7 bar nitrogen wasapplied to keep the feed in the liquid state.

    ______________________________________                                               Temp     Total Feed Flow Rate                                                                         TAME weight %                                  Run No °C.                                                                             g hour.sup.-1  in product                                     ______________________________________                                        1      50       27             0.3                                            2      70       11             1.0                                            3      70        7             1.1                                            4      95       11             3.0                                            ______________________________________                                    

Under these conditions no dimers of the C₅ hydrocarbons or dimethylether were produced.

This example demonstrates that NU-87 can act as a catalyst for thereaction of substituted olefins with methanol to produce ethers.

EXAMPLE 26 Propane Aromatisation

2.61 g of the material from Example 16 was refluxed with 7.2 ml of a0.1M solution of Ga(NO₃)₃ diluted with 70 ml of deionised water, for 26hours. Water was removed by rotary evaporation. The resulting powder waspelleted, broken down and sieved to give a 500 to 1000 micron sizefraction. This fraction was then calcined in a tube furnace, under astream of dry air (at a rate of 7 dm³ per hour) at 530° C. for 10hours). The resultant catalyst was analysed by AAS and found to contain1.97% by weight gallium.

0.934 g of the catalyst was transferred to a stainless steel reactor(internal diameter of 4.6 mm) and supported on glass wool and glassballs. The catalyst bed was dehydrated for 1 hour at 530° C. under astream of nitrogen.

A feed of pure propane gas was passed over the catalyst bed at a feedflow rate of 0.778 dm³ per hour and a weight hourly space velocity of1.53 hr⁻¹. The catalyst bed was maintained at 530° C. and atmosphericpressure, and the resulting gaseous products were analysed by gaschromatography. A gas analysis, after the catalyst had been on line atthe reaction temperature for 30 minutes, showed that 34% of the propanefeed was being converted. The concentration of benzene in the gaseoushydrocarbon products was 14.4 wt %, the concentration of toluene was17.6 wt %, and the corresponding total concentration of xylene isomerswas 6.2 wt %. Therefore, the total concentration of aromatics in thegaseous hydrocarbon products was 38.1 wt %.

This example demonstrates illustrates the use of a gallium impregnatedzeolite NU-87 in the aromatisation of propane.

EXAMPLE 27 Preparation of Amines

A portion of the material from Example 16 was pelleted, broken down andsieved to give a 500-1000 micron size fraction. A sample of thismaterial (3.42 g) was charged to a tubular stainless steel microreactorand heated to 300° C. under a flow of nitrogen before the reactant gaseswere introduced. The feed consisted of a gaseous mixture of ammonia andmethanol and conditions were adjusted to give the desired methanolconversion. The reaction products were measured by on-line gaschromatography and found to consist of a mixture of mono-, di-andtri-methylamines. At a temperature of 350° C. using a feed containing amolar ratio of ammonia to methanol of 2.25 at a gas hourly spacevelocity (GHSV) of 1450 hr⁻¹ the methanol conversion was 98% and theproduct consisted of 45 mole % monomethylamine, 27 mole % dimethylamineand 28 mole % trimethylamine. At the same temperature using a molarratio of ammonia of methanol of 2.6 at GHSV 1480 hr⁻¹, the methanolconversion was 99% and the product composition 48 mole %monomethylamine, 26 mole % dimethylamine and 26 mole % trimethylamine.

This example demonstrates the use of zeolite NU-87 as a catalyst for thepreparation of amines.

EXAMPLE 28 Fluid Catalytic Cracking Additive

Zeolite NU-87 was evaluated as a fluid catalytic cracking (FCC) additiveby adding it in small quantities to a base FCC catalyst and thenmonitoring its effect on the cracking products in a microactivity test(MAT) run.

Base Catalyst

The base FCC catalyst used was Resoc-1, E-Cat (Grace Davidson). The"E-Cat" indicates that the catalyst has been deactivated on line in aFCC plant. The base catalyst was decoked by calcining in air for 24hours at 550° C. Resoc-1 is a rare earth exchanged Ultrastabilised Yzeolite based catalyst in spray dried form.

Additive Catalyst

Each sample of NU-87 was tested by preparing two catalysts.

(a) Resoc-1, E-Cat+1% by weight fresh NU-87 based on the weight ofResoc-1, E-Cat

(b) Resoc-1, E-Cat+2% by weight fresh NU-87 based on the weight ofResoc-1, E-Cat

(the % weight of NU-87 are based on anhydrous material).

Individual catalysts were prepared by thorough physical mixing of thebase catalyst with a portion of material from Example 2. The mixture wasthen compressed. The resulting pellet was broken up and sieved to givegranules with a size in the range of 44 to 70 microns.

The feedstock used in these experiments was Cincinnati gas oil. Theproperties of this material are as follows.

    ______________________________________                                        Vacuum Distillation  °C.                                               ______________________________________                                        10% at 760 mm        312.7  (595° F.)                                  30%                  362.8  (685° F.)                                  50%                  407.2  (765° F.)                                  70%                  451.7  (845° F.)                                  80%                  501.1  (934° F.)                                  ______________________________________                                    

The MAT runs were carried out in a fixed bed unit using a 3 ml charge ofCincinnati gas oil. The weight hourly space velocity (WHSV) ofindividual runs is given in Table 17.

The catalyst samples had all been calcined in air at 538° C. for 1 hourbefore testing. The starting temperature for each run was 515.6° C.

The products were analysed by gas chromatography capillary columnanalysis from which the research octane number (RON) of the resultinggasoline could be determined. Table 17 lists this data.

From results given in Table 17 it can be seen that the addition ofzeolite NU-87 increases the RON of gasoline. It also increases the yieldof C₃ and C₄ paraffins and olefins.

EXAMPLE 29 Dewaxing of a Feedstock

A portion of the material from Example 14 was activated in a mannersimilar to that described in Example 15. Analysis for Na, Si and Al byAAS gave the following molar composition:

    37.1 SiO.sub.2 --Al.sub.2 O.sub.3 --less than 0.003Na.sub.2 O

A 24.6 gram sample of this activated material was added to 200 ml of a1M solution of nickel nitrate in deionised water. The resulting slurrywas heated at 90° C. for 3.5 hours. The nickel nitrate solution was thenseparated by centrifuging and the zeolite powder subsequently dried at90° C.

The zeolite powder was then nickel exchanged a second time using a freshportion of the nickel nitrate solution. This gave nickel exchangedzeolite product A.

This procedure was repeated with a second 20.5 g sample of the activatedmaterial. This gave nickel exchanged zeolite product B. Products A and Bwere combined and calcined in static air as follows:

(a) temperature increasing from 25° to 150° C. over a period of 1 hour;

(b) 150° C. for 1 hour;

(c) temperature increasing from 150° to 350° C. over a period of 1 hour;

(d) 350° C. for 1 hour;

(e) temperature increasing from 350° to 540° C. over a period of 2hours; and

f) 540° C. for 16 hours.

The resulting catalyst was analysed by AAS and found to contain 1.45% byweight of nickel.

A 25 g portion of the catalyst was reduced in a flow of hydrogen at 371°C. for 2 hours and then sulphided by passing over it a flow of 2%hydrogen sulphide in hydrogen at 371° C. for 2 hours. 150 ml of thefeedstock described below was then added to the catalyst in a 300 mlautoclave. The pressure was increased to 400 psig, using hydrogen, andthe temperature increased to 316° C. The autoclave was maintained for 2hours at this temperature and pressure. (The pressure was maintainedusing a 15 dm³ /hour flow of hydrogen).

The pour point of the resulting dewaxed product was found to be -12.2°C. This represents a reduction of 19.4° C. in the pour point offeedstock. Thus, this example demonstrates the utility of a nickelexchanged NU-87 in dewaxing of a feedstock.

A heavy gas oil sample was used as feedstock. Its properties are asfollows:

    ______________________________________                                        Density (at 15° C., g/ml)                                                                  0.8556                                                    Pour Point, °C.                                                                            +7.2                                                      Cloud Point, °C.                                                                           +18                                                       Sulphur, wt %       0.16                                                      Simulated Distillation, °C.                                            Initial Boiling point                                                                             119                                                        5%                 232                                                       10%                 262                                                       20%                 288                                                       30%                 304                                                       40%                 319                                                       50%                 332                                                       60%                 346                                                       70%                 361                                                       80%                 379                                                       90%                 404                                                       95%                 422                                                       Final Boiling Point 458                                                       ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                        Product Composition in toluene disproportionation over NU-87                  Time (hr)                                                                               2       5      10    25   50   100  150                             Temp (°C.)                                                                      350     350    350   350  350   352  357                             ______________________________________                                        C1-C4    0.34    0.20   0.13  0.09 0.08  0.07 0.08                            hydrocarbons                                                                  (wt %)                                                                        Benzene  24.04   23.52  22.82 22.13                                                                              21.41 20.58                                                                              20.93                           (wt %)                                                                        Toluene  45.28   46.83  48.67 50.58                                                                              51.89 53.67                                                                              53.11                           (wt %)                                                                        Ethyl-   0.37    0.22   0.14  0.09 0.08  0.06 0.07                            benzene                                                                       (wt %)                                                                        Xylenes  24.57   24.70  24.30 23.72                                                                              23.38 22.83                                                                              22.91                           (wt %)                                                                        C9+      5.39    4.52   3.94  3.38 3.16  2.77 2.90                            Aromatic                                                                      (wt %)                                                                        Conversion                                                                             54.72   53.17  51.33 49.42                                                                              48.11 46.33                                                                              46.89                           (wt %)                                                                        ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                        Hydroisomerisation of xylenes over Nu-87                                      Time (hr)           29     51  144  146  191  240                             Temp (°C.)                                                                        (feed)  400    450  450  480  480  480                             ______________________________________                                        WHSV               43.3   43.3 43.3 43.3 43.3 52.8                            Gas (wt %)         0.08   0.13 0.10 0.20 0.19 0.17                            Benzene (wt %)     0.16   0.24 0.19 0.41 0.44 0.36                            Toluene (wt %)                                                                           0.05    2.94   1.32 0.66 1.43 2.11 1.43                            Ethylbenzene                                                                             4.50    3.47   3.78 4.08 3.61 3.39 3.63                            (wt %)                                                                        P Xylene (wt %)                                                                          9.38    19.93  20.44                                                                              20.09                                                                              21.88                                                                              21.89                                                                              22.13                           M Xylene (wt %)                                                                          57.42   47.53  48.81                                                                              49.88                                                                              48.37                                                                              47.82                                                                              48.36                           O Xylene (wt %)                                                                          28.65   22.55  24.08                                                                              24.45                                                                              22.76                                                                              21.98                                                                              22.48                           C9+ Aromatic       3.33   1.18 0.55 1.34 2.18 1.45                            (wt %)                                                                        % P Xylene made    10.55  11.06                                                                              10.71                                                                              12.50                                                                              12.51                                                                              12.75                           % Xylenes lost     5.69   2.22 1.09 2.55 3.93 2.61                            % Ethylbenzene     22.90  15.91                                                                              9.24 19.79                                                                              24.65                                                                              19.34                           lost                                                                          ______________________________________                                    

                  TABLE 13                                                        ______________________________________                                        Low Pressure Isomerisation of Xylenes over Nu-87                              WHSV: 36.4 hr.sup.-1  Temperature: 350° C.                                                  Products                                                                Feed  at 10 hours                                                             (wt %)                                                                              on line (wt %)                                           ______________________________________                                        Gas                      0.06                                                 Benzene                  0.19                                                 Toluene          0.05    6.31                                                 Ethylbenzene     4.50    2.95                                                 P Xylene         9.38    18.68                                                M Xylene         57.42   44.35                                                O Xylene         28.65   19.90                                                C9+ Aromatic             7.56                                                 % P Xylene made          9.28                                                 % Xylene lost            13.12                                                % Ethylbenzene lost      34.39                                                ______________________________________                                    

                  TABLE 14                                                        ______________________________________                                        Methylation of toluene in the presence of hydrogen                            Time (hours)                                                                               1      4      7    23   25   28   29                             Temperature (°C.)                                                                  325    350    370  390  420  440  460                             ______________________________________                                        Benzene (% wt)                                                                            0.35   0.76   0.43 0.14 0.83 1.05 2.11                            Toluene (% wt)                                                                            82.32  81.70  81.68                                                                              89.68                                                                              79.96                                                                              81.05                                                                              73.85                           P-Xylene (% wt)                                                                           3.06   3.29   3.31 2.08 3.53 3.49 4.58                            M-Xylene (% wt)                                                                           3.73   4.89   4.60 2.69 6.43 6.55 9.49                            O-Xylene (% wt)                                                                           6.25   4.89   6.10 3.92 4.98 4.32 4.42                            C9+ Aromatic                                                                              4.29   4.48   3.88 1.48 4.28 3.54 5.49                            (% wt)                                                                        Tot Xylenes (% wt)                                                                        13.03  13.07  14.01                                                                              8.69 14.94                                                                              14.36                                                                              18.49                           % O-Xylene in                                                                             48.00  37.39  43.54                                                                              45.15                                                                              33.31                                                                              24.32                                                                              23.91                           xylenes                                                                       ______________________________________                                    

                  TABLE 15                                                        ______________________________________                                        Methylation of Toluene at atmospheric pressure                                Time (hours)      1      4        23   29                                     Temperature (°C.)                                                                       300    300      300  335                                     ______________________________________                                        WHSV (hr.sup.-1) 34.6   8.7      8.7  8.7                                     Benzene (% wt)   0.47   0.31     0.18 0.64                                    Toluene (% wt)   83.98  83.64    91.14                                                                              77.67                                   P-Xylene (% wt)  3.01   3.08     1.92 3.89                                    M-Xylene (% wt)  3.05   3.02     1.57 5.21                                    O-Xylene (% wt)  6.42   6.68     4.13 7.50                                    C9+ Aromatic (% wt)                                                                            3.06   3.27     1.06 5.09                                    Tot Xylenes (% wt)                                                                             12.48  12.78    7.62 16.60                                   % O-Xylene in Xylenes                                                                          51.46  52.25    54.18                                                                              45.19                                   ______________________________________                                    

                  TABLE 16                                                        ______________________________________                                        Ethylation of Benzene                                                         Time (hr)        6      12       18   24                                      ______________________________________                                        Ethylene (wt %)  0.54   0.68     7.41 10.81                                   Benzene (wt %)   61.84  61.80    71.43                                                                              77.92                                   Toluene (wt %)   0.07   0.00     0.00 0.00                                    Ethylbenzene (wt %)                                                                            27.45  28.10    16.47                                                                              10.03                                   Orthoxylene (wt %)                                                                             0.16   0.14     0.07 0.00                                    C9+ Aromatics (wt %)                                                                           9.95   9.29     4.63 1.23                                    % EB in Products 72.8   74.9     77.8 89.1                                    % EB in C8 Arom  99.4   99.5     99.6 99.9                                    ______________________________________                                    

                  TABLE 17                                                        ______________________________________                                        Fluid Catalytic Cracking Additive                                             ______________________________________                                                      (Comparative)                                                   Catalyst      Resoc-1, E-CAT                                                                             a        b                                         ______________________________________                                        WHSV (hr.sup.-1)                                                                            15.74        15.97    16.07                                     Temperature                                                                   Starting      515.6° C.                                                                           515.6° C.                                                                       515.6° C.                          lowest        501.1° C.                                                                           496.7° C.                                                                       490° C.                            ______________________________________                                                      Wt %         Wt %     Wt %                                      ______________________________________                                        Conversion    63.23        62.82    61.78                                     Product Yields                                                                Total C3's    4.44         6.77     7.72                                      Propane       .84          1.49     1.98                                      Propylene     3.60         5.29     5.74                                      Total C4's    8.40         11.84    12.76                                     I-Butane      3.45         5.29     5.72                                      N-Butane      .67          .94      1.14                                      Total Butenes 4.29         5.60     5.89                                      1-Butene      2.01         2.86     3.15                                      Trans-Butenes 1.31         1.58     1.58                                      Cis-Butenes   .96          1.16     1.16                                      BP range C.sub.5-                                                                           44.11        37.20    33.55                                     430° F. Gasoline                                                       BP range 430- 22.43        22.24    22.49                                     650° F. Light Cycle                                                    Gas Oil                                                                       BP range 650° F. and                                                                 14.34        14.94    15.73                                     above Diesel Oil                                                              FCC Gasoline + Alkyl-                                                                       76.83        77.60    75.31                                     ate (VOL %)                                                                   Research Octane Num-                                                                        93.3         97.2     99.6                                      ber (Gasoline)                                                                ______________________________________                                         BP = boiling point                                                       

We claim:
 1. A catalyst comprising a zeolite designated NU- 87 saidzeolite having a composition expressed on an anhydrous basis (in termsof mole ratios of oxide) by the formula

    100 XO.sub.2 : equal to or less than 10 Y.sub.2 O.sub.3 : equal to or less than 20 R.sub.2/n O

wherein R is at least partly hydrogen, X is silicon and/or germanium, Yis one or more of aluminium, iron, gallium, boron, titanium, vanadium,zirconium, molybdenum, arsenic, antimony, chromium and manganese andhaving an X-ray diffraction pattern including the lines shown in Table2.
 2. A catalyst as claimed in claim 1 in which the hydrogen ispartially or completely replaced by a metal.
 3. A catalyst as claimed inclaim 1 or claim 2 further comprising a component selected from(a) abinder; (b) a catalyst support material; (c) a further zeolite or amolecular sieve; (d) a metal; and (e) a further catalystor a combinationthereof.
 4. A catalyst as claimed in claim 1 where X is silicon and Y isaluminium.
 5. A method for preparing a catalyst as claimed in claim 2 orclaim 3 comprising(a) impregnation of the zeolite as defined in claim 1with a metal compound or (b) subjecting the zeolite as defined in claim1 to ion-exchange with a metal ion.